CN109534460A - A kind of Ti electrode and the preparation method and application thereof - Google Patents
A kind of Ti electrode and the preparation method and application thereof Download PDFInfo
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- CN109534460A CN109534460A CN201811596201.7A CN201811596201A CN109534460A CN 109534460 A CN109534460 A CN 109534460A CN 201811596201 A CN201811596201 A CN 201811596201A CN 109534460 A CN109534460 A CN 109534460A
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- Prior art keywords
- titanium
- silver
- middle layer
- electrode
- bismuth
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 127
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 30
- PEXQGCJZJMEHKN-UHFFFAOYSA-N [Ti].[Sn].[Bi] Chemical compound [Ti].[Sn].[Bi] PEXQGCJZJMEHKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 239000002585 base Substances 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000005554 pickling Methods 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005422 blasting Methods 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 230000001680 brushing effect Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 238000001548 drop coating Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims 1
- 238000004544 sputter deposition Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- 239000002351 wastewater Substances 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 238000002161 passivation Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000002604 ultrasonography Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QAKMMQFWZJTWCW-UHFFFAOYSA-N bismuth titanium Chemical compound [Ti].[Bi] QAKMMQFWZJTWCW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical group [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention provides a kind of Ti electrodes and the preparation method and application thereof, belong to electrode technology field.The Ti electrode includes Titanium base, silver-colored middle layer and bismuth titanium tin active layer；Silver-colored middle layer is set to the surface of Titanium base, and bismuth titanium tin active layer is set to the surface of the side of the separate Titanium base of silver-colored middle layer.Ti electrode oxygen evolution potential with higher and longer working life.Preparation method includes: to prepare silver-colored middle layer in the surface of Titanium base, and bismuth titanium tin active layer is arranged in the surface of the side of the separate Titanium base of silver-colored middle layer, is then made annealing treatment.This method simple process, favorable repeatability is easily operated, can effectively delay the passivation speed of Titanium base, extend the working life of electrode, while making electrode oxygen evolution potential with higher.The Ti electrode can be used for various wastewater processing environment, pollutant that can effectively in degrading waste water.
Description
Technical field
The invention belongs to electrode technology fields, and in particular to a kind of Ti electrode and the preparation method and application thereof.
Background technique
Coated titanium electrode, also referred to as dimensional stable anode are widely used in chlorine industry, wastewater treatment, plating, cathode guarantor
The numerous areas such as shield.
Currently, common tin oxide electrode working life is short in coated titanium electrode, its large-scale application is seriously limited.
Therefore, a kind of new coated titanium electrode that can replace tin oxide electrode need to be developed.
Summary of the invention
An object of the present invention includes providing a kind of Ti electrode, Ti electrode oxygen evolution potential with higher and longer
Working life.
The second object of the present invention includes providing a kind of preparation method of above-mentioned Ti electrode, the preparation method simple process,
Favorable repeatability, it is easily operated, it can effectively delay the passivation speed of Titanium base, extend the working life of electrode, while make electricity
Oxygen evolution potential extremely with higher.
The third object of the present invention includes providing a kind of application of above-mentioned Ti electrode, such as can be used for wastewater treatment.
The present invention solves its technical problem and adopts the following technical solutions to realize:
The embodiment of the present invention proposes a kind of Ti electrode, which includes that Titanium base, silver-colored middle layer and bismuth titanium tin are living
Property layer；Silver-colored middle layer is set to the surface of Titanium base, and bismuth titanium tin active layer is set to the side of the separate Titanium base of silver-colored middle layer
Surface.
The invention also provides a kind of preparation methods of above-mentioned Ti electrode, comprising the following steps: in the surface system of Titanium base
Standby silver middle layer is arranged bismuth titanium tin active layer in the surface of the side of the separate Titanium base of silver-colored middle layer, then carries out at annealing
Reason.
The invention also provides a kind of applications of above-mentioned Ti electrode, such as can be used for wastewater treatment.
The beneficial effect of Ti electrode and the preparation method and application thereof includes: in the embodiment of the present invention
The Ti electrode oxygen evolution potential with higher and longer working life that present pre-ferred embodiments provide.It is made
Preparation Method simple process, favorable repeatability is easily operated, can effectively delay the passivation speed of Titanium base, extend the work of electrode
Make the service life, while making electrode oxygen evolution potential with higher.The Ti electrode can be used for wastewater treatment, can be effectively in degrading waste water
Pollutant.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the volt-ampere performance map for the Ti electrode that embodiment 1 provides in the application test example 1；
Fig. 2 is the current potential-time diagram for the Ti electrode that embodiment 1 provides in the application test example 1.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Technical scheme is described in detail below.
This application involves Ti electrode include Titanium base, silver-colored middle layer and bismuth titanium tin active layer；Silver-colored middle layer is set to
The surface of Titanium base, bismuth titanium tin active layer are set to the surface of the side of the separate Titanium base of silver-colored middle layer.
Through inventors have found that the short reason of currently used tin oxide electrode working life may is that in catalysis oxidation mistake
Cheng Zhong can generate layer of titanium dioxide passivating film between stannic oxide materials and matrix, the passivating film hinder electronics transfer into
Row, eventually leads to the inactivation of electrode.In consideration of it, inventor between matrix and bismuth titanium tin active layer in this application by being added
The middle layer that oxygen atom and Titanium base can be prevented to contact, to improve electrode working life.
Set silver-colored middle layer for middle layer, can make the middle layer have stronger chemical stability, acid-alkali-corrosive-resisting and
It is not oxidizable, and silver is more preferably cheap compared with platinum group metal price.Further, active layer is collectively formed in bismuth, titanium and tin, in
Interbed has stronger binding force, makes entire electrode structure close and firm, and the active layer mixes oxidation relative to traditional antimony
Tin coating is more stable, can make Ti electrode oxygen evolution potential with higher, to possess stronger catalytic capability.
In the application, the thickness of silver-colored middle layer can be 1-106Nm, as 1nm, 10nm, 50nm, 100nm, 500nm,
1000nm、5000nm、104nm、5×104nm、105nm、5×105Nm or 106Nm etc., or 1-106Appointing within the scope of nm
One thickness value.
Further, the thickness of silver-colored middle layer can be 102-105Nm, further, the thickness of silver-colored middle layer can be
103-104nm。
In some embodiments, silver-colored middle layer and the overall thickness of bismuth titanium tin active layer are no more than 10 μm, such as can be 2
μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm etc..
In this application, the molar ratio of the bismuth in bismuth titanium tin active layer, titanium and tin can be 1-10:20-50:70-100,
Namely the molar ratio in bismuth titanium tin active layer between the molar ratio of bismuth, the molar ratio of titanium and tin can be respectively in 1-10,20-50
And it is freely combined in the range of 70-100, such as molar ratio between three can be 1:20:70,1:50:100,10:20:
70,10:50:100 or 5:35:85 etc..
In this application, Titanium base includes titanium plate, titanium net or stud, and size can be determined according to actual use situation.
In addition, present invention also provides a kind of preparation methods of above-mentioned Ti electrode, it may include following steps: in Titanium base
Surface prepares silver-colored middle layer, and bismuth titanium tin active layer is arranged in the surface of the side of the separate Titanium base of silver-colored middle layer, then carries out
Annealing.
Wherein, the preparation of silver-colored middle layer includes: using such as magnetron sputtering method, galvanoplastic, evaporation coating method or chemical gas
The methods of phase sedimentation forms the silver-colored middle layer of required thickness in the surface coverage silver of Titanium base.
It in some embodiments, further include being pre-processed to Titanium base before silver-colored middle layer is set.Pre-process example
It such as may include: that polishing or blasting treatment, alkali cleaning and pickling are carried out to Titanium base.
Optionally, polishing can be is rubbed Titanium base repeatedly with the sand paper of 40-800 mesh, until Titanium base shows
Metallic luster.Blasting treatment, which can be, gets Titanium base surface uniformly densely covered pockmark with quartz sand.Pass through polishing or sandblasting
Processing can remove the impurity and titanium oxide of the attachment of Titanium base surface, and can also increase the ratio of Titanium base by blasting treatment
Surface area improves the adhesive force of coating.
Optionally, alkali cleaning can be adds in the NaOH solution that concentration is 20-40wt% under conditions of 80-95 DEG C
Hot 1-3h；Or it is cleaned by ultrasonic 10-30min in acetone soln, by alkali cleaning to remove the organic matters such as the grease on Titanium base.
Preferably, pickling can be under conditions of 80-95 DEG C in the oxalic acid or 45-55vol% that concentration is 10-40wt%
1-3h is heated in the hydrochloric acid solution of (preferably 50vol%).Rough fiber crops are gone out with the surface etch in Titanium base by pickling
Face enhances the binding force of coating and matrix.Titanium base can be dried up with nitrogen stream after pickling.
Further, the preparation of bismuth titanium tin active layer may include: that the precursor liquid containing bismuth, titanium and tin is covered in silver
The surface of the side of the separate Titanium base of interbed is to form bismuth titanium tin active layer.Wherein, covering method may include but not only limit
In brushing method, drop-coating, dip-coating method, spin-coating method, electrodeposition process, magnetron sputtering method or vapour deposition method.
In some embodiments, precursor liquid can be by BiCl3、SnCl2·2H2O and butyl titanate are in dehydrated alcohol
It is mixed under conditions of solvent.Specifically, it such as can be BiCl3And SnCl2·2H2O is dissolved in dehydrated alcohol, then
Butyl titanate is added, precursor liquid then can be obtained with ethyl alcohol constant volume.
Further, it after brushing precursor liquid, is made annealing treatment, so that non-oxidized substance is completely converted into oxide and shape
The electrode being firmly combined at each layer.Optionally, annealing can be in 450-600 DEG C of (such as 450 DEG C, 480 DEG C, 500
DEG C, 520 DEG C, 550 DEG C, 580 DEG C or 600 DEG C etc.) under conditions of carry out.It is worth noting that annealing atmosphere can be in atmosphere
It is carried out under environment, is also possible to carry out in oxygen atmosphere.
It holds, the application is by preparing bismuth titanium in one layer of silver-colored middle layer of Titanium base surface plating, then on the surface of silver-colored middle layer
Tin active layer can make the more existing electrode of electrode obtained not only have great promotion (such as can be more general in working life
Logical Ti/Sb-SnO25 times of electrode lifting or so), at the same also have oxygen evolution potential (such as with 0.5mol/L sulfuric acid be electrolysis
Liquid can achieve the oxygen evolution potential of 2.0V when Mercurous sulfate electrode is as reference electrode).
In addition, present invention also provides a kind of applications of above-mentioned Ti electrode, such as it can be used for wastewater treatment, it can be effective
Pollutant in degrading waste water.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Titanium base pretreatment:
Titanium-based piece is successively polished with 80 mesh and 400 mesh sand paper repeatedly, until titanium plate shows metallic luster.It will polish
Titanium-based piece be placed in the NaOH solution of 40wt% with deionized water ultrasound 10min, heat 1h under 95 DEG C of water bath condition.
By titanium sheet taking-up deionized water ultrasound 10min after alkali cleaning, then titanium sheet is placed in the HCl solution of 50vol%, in 90 DEG C of water
It is kept for 1 hour under the conditions of bath.It is cleaned by ultrasonic after pickling with deionized water, then is dried up with nitrogen stream.
The preparation of middle layer:
By magnetron sputtering method, the silver-colored middle layer of 100nm thickness is prepared on the Titanium base handled well.Background is true when deposition
Sky is 4.5 × 10-4Pa, the flow for being passed through argon gas is 20sccm, and operating air pressure is controlled in 0.5Pa.Substrate temperature is when deposition
25℃。
The preparation of active layer:
Accurately weigh the BiCl of 1.5767g3With the SnCl of 11.2825g2·2H2O is dissolved in 30ml dehydrated alcohol, into solution
The butyl titanate of 5.1054g is added, transfers the solution into 50ml volumetric flask, ethyl alcohol constant volume is added, precursor liquid is made.
Appropriate precursor liquid is dipped with hairbrush, is brushed repeatedly in the titanium plate of the good silver-colored middle layer of plating, it is whole to masking liquid uniform fold
After a titanium plate, titanium plate is placed in in 100 DEG C of drying box dry 5min, is placed in 500 DEG C of Muffle furnace annealing 5min after taking-up again.
Above-mentioned coating procedure is repeated 20 times, and last time annealing is kept for 1 hour.After taking-up natural cooling to get arrive required electrode.
Embodiment 2
Titanium base pretreatment:
Titanium-based piece is done into blasting treatment with 220 mesh quartz sands.By blasting treatment good titanium-based piece deionized water ultrasound
10min is placed in acetone soln, ultrasonic 40min.By titanium sheet taking-up deionized water ultrasound 10min after deoiling, then by titanium sheet
It is placed in the oxalic acid solution of 10wt%, is kept for 1 hour under 95 DEG C of water bath condition.Titanium plate is surpassed in deionized water after pickling
Sound cleaning, then it is spare with nitrogen stream drying.
The preparation of middle layer:
By electrodeposition process, the silver-colored middle layer with a thickness of 1000nm is prepared on the Titanium base handled well.It is with purity
For 99.99% silver foil as anode, Titanium base is cathode, and electrolyte is silver chlorate (30g/L), potassium cyanide (60g/L), potassium carbonate
The mixed solution of (15g/L), current density 10mA/cm2, deposit 60s.
The preparation of active layer:
Accurately weigh the BiCl of 1.5767g3With the SnCl of 11.2825g2·2H2O is dissolved in 30ml dehydrated alcohol, into solution
The butyl titanate of 5.1054g is added, transfers the solution into 50ml volumetric flask, ethyl alcohol constant volume is added, precursor liquid is made.
The titanium plate handled well is placed on vacuum spin coater, the precursor liquid prepared in right amount is added dropwise with suction pipe, spin coater is set
Revolving speed 2500r/min rotates 30s, and then the titanium plate coated is placed in in 80 DEG C of drying box dry 10min, set again after taking-up
In 550 DEG C of Muffle furnace annealing 5min.Above-mentioned coating procedure is repeated 20 times, and last time annealing keeps 1h.It is naturally cold after taking-up
But to get arrive required electrode.
Embodiment 3
Titanium base pretreatment:
40 mesh of titanium net and 800 mesh sand paper are polished repeatedly, until titanium net shows metallic luster.The titanium net that will have been polished
It is placed in the NaOH solution of 20wt% with deionized water ultrasound 20min, heats 3h under 80 DEG C of water bath condition.It will after alkali cleaning
Titanium net, which is taken out, uses deionized water ultrasound 10min, then titanium net is placed in the HCl solution of 10wt%, under 80 DEG C of water bath condition
It is kept for 3 hours.It is cleaned by ultrasonic after pickling with deionized water, then is dried up with nitrogen stream.
The preparation of middle layer:
It is prepared by galvanoplastic on the Titanium base handled well with a thickness of 105The silver-colored middle layer of nm.
The preparation of active layer:
Weigh BiCl3And SnCl2·2H2O is dissolved in dehydrated alcohol, and butyl titanate is added into solution, transfers the solution into
In 50ml volumetric flask, ethyl alcohol constant volume is added, the molar ratio that bismuth, titanium and tin is made is 1:20:70 precursor liquid.
Precursor liquid is deposited on to the surface of the side of the separate titanium net of silver-colored middle layer using electrodeposition process, is then dried
10min, then it is placed in 450 DEG C of Muffle furnace annealing 8min.Above-mentioned coating procedure repeats 25 times, and last time annealing keeps 1h.It takes
Out after natural cooling to get arrive required electrode.Wherein, silver-colored middle layer and the overall thickness of bismuth titanium tin active layer are 2 μm.
Embodiment 4
Titanium base pretreatment:
200 mesh of stud and 400 mesh sand paper are polished repeatedly, until stud shows metallic luster.The titanium that will have been polished
Stick is placed in the NaOH solution of 30wt% with deionized water ultrasound 20min, heats 2h under 90 DEG C of water bath condition.After alkali cleaning
It is placed in the oxalic acid solution of 25wt% by stud taking-up deionized water ultrasound 10min, then by stud, in 95 DEG C of water bath condition
It is lower to be kept for 2 hours.It is cleaned by ultrasonic after pickling with deionized water, then is dried up with nitrogen stream.
The preparation of middle layer:
It is prepared by evaporation coating method on the Titanium base handled well with a thickness of 104The silver-colored middle layer of nm.
The preparation of active layer:
Weigh BiCl3And SnCl2·2H2O is dissolved in dehydrated alcohol, and butyl titanate is added into solution, transfers the solution into
In 50ml volumetric flask, ethyl alcohol constant volume is added, the molar ratio that bismuth, titanium and tin is made is 10:50:100 precursor liquid.
Precursor liquid is deposited on to the surface of the side of the separate stud of silver-colored middle layer using magnetron sputtering method, is then dried
10min, then it is placed in 600 DEG C of Muffle furnace annealing 10min.Above-mentioned coating procedure repeats 25 times, and last time annealing keeps 1h.It takes
Out after natural cooling to get arrive required electrode.Wherein, silver-colored middle layer and the overall thickness of bismuth titanium tin active layer are 5.5 μm.
Embodiment 5
The present embodiment the difference from embodiment 1 is that: the molar ratio of bismuth, titanium and tin in bismuth titanium tin active layer be 5:35:
85。
Test example
By taking the resulting electrode of embodiment 1 as an example, it is tested for the property, test selection is standard three electrode system electricity
Xie Chi, being tested electrode is working electrode, selects platinum electrode to electrode, mereurous sulfate is as reference electrode, electrolyte
The sulfuric acid solution of 0.5mol/L.In reinforcing life test, current density 100mA/cm2, press raising 5V to be counted as electrode with slot and lose
It is living.Its result is as depicted in figs. 1 and 2.As seen from Figure 1, the oxygen evolution potential of the electrode is 2.0V.As seen from Figure 2, electric
The reinforcing service life of pole is about 27 hours.
Control group 1-2 is set, control group 1 the difference from embodiment 1 is that without silver-colored middle layer, control group 2 and embodiment 1
Difference is that the material of active layer is that antimony mixes tin oxide, comparative example 1 and control group 1, the resulting electrode of control group 2 it is related
Performance, the results are shown in Table 1.
1 electrode performance of table
| Embodiment 1 | Control group 1 | Control group 2 | |
| Oxygen evolution potential | 2.0V | 1.9V | 2.0V |
| Service life | 27h | 3h | 5h |
As can be seen from Table 1, by silver-colored middle layer being arranged again between Titanium base and active layer or will be intermediate in the application
The active constituent of layer by three kinds of bismuth, titanium and tin substances with being combined into, can significantly improve resulting Ti electrode oxygen evolution potential and
Service life.
To sum up, Ti electrode provided by the present application oxygen evolution potential with higher and longer working life.Its preparation side
Method simple process, favorable repeatability is easily operated, can effectively delay the passivation speed of Titanium base, extends the work longevity of electrode
Life, while making electrode oxygen evolution potential with higher.The Ti electrode can be used for wastewater treatment, pollution that can effectively in degrading waste water
Object.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of Ti electrode, which is characterized in that the Ti electrode includes Titanium base, silver-colored middle layer and bismuth titanium tin active layer；Institute
The surface that silver-colored middle layer is set to the Titanium base is stated, the bismuth titanium tin active layer is set to the separate described of the silver-colored middle layer
The surface of the side of Titanium base.
2. Ti electrode according to claim 1, which is characterized in that it is described silver middle layer with a thickness of 1-106nm；
Preferably, the silver-colored middle layer and the overall thickness of the bismuth titanium tin active layer are no more than 10 μm.
3. Ti electrode according to claim 1, which is characterized in that bismuth, titanium and tin in the bismuth titanium tin active layer rub
You are than being 1-10:20-50:70-100.
4. Ti electrode according to claim 1, which is characterized in that the Titanium base includes titanium plate, titanium net or stud.
5. the preparation method of Ti electrode according to any one of claims 1-4, which comprises the steps of: in institute
The surface for stating Titanium base prepares the silver-colored middle layer, is arranged in the surface of the side far from the Titanium base of the silver-colored middle layer
The bismuth titanium tin active layer, is then made annealing treatment.
6. preparation method according to claim 5, which is characterized in that the preparation of the silver middle layer includes: using magnetic control
Sputtering method, galvanoplastic, evaporation coating method or chemical vapour deposition technique are in the surface coverage silver of the Titanium base to form the silver
Middle layer.
7. preparation method according to claim 5, which is characterized in that the preparation of the bismuth titanium tin active layer includes: that will contain
There is the precursor liquid of bismuth, titanium and tin to be covered in the surface of the side far from the Titanium base of the silver-colored middle layer to form the bismuth
Titanium tin active layer；Covering method include brushing method, drop-coating, dip-coating method, spin-coating method, electrodeposition process, magnetron sputtering method or
Vapour deposition method；
Preferably, the precursor liquid is by BiCl3、SnCl2·2H2O and butyl titanate are mixed under conditions of dehydrated alcohol is solvent
It closes.
8. preparation method according to claim 5, which is characterized in that annealing carries out under conditions of 450-600 DEG C.
9. preparation method according to claim 5, which is characterized in that further include pair before the silver-colored middle layer is arranged
The Titanium base is pre-processed；
Pretreatment includes: to carry out polishing or blasting treatment, alkali cleaning and pickling to the Titanium base；
Preferably, alkali cleaning is to heat 1-3h in the NaOH solution that concentration is 20-40wt% under conditions of 80-95 DEG C；Or, alkali
Wash is to be cleaned by ultrasonic 10-30min in acetone soln；
Preferably, pickling is molten in the hydrochloric acid of oxalic acid or 45-55vol% that concentration is 10-40wt% under conditions of 80-95 DEG C
1-3h is heated in liquid.
10. a kind of application of Ti electrode according to any one of claims 1-4, which is characterized in that the Ti electrode is for giving up
Water process.
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